JP3524670B2 - Methanol synthesis catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to hydrogen (H_Two) And one
Methanol from gas containing carbon oxide (CO) as a main component
It relates to the catalyst to be synthesized. [0002] [Prior Art] Is the development research of methanol synthesis catalyst old?
Zinc oxide-chromium oxide, copper oxide-oxidation
A catalyst having a composition such as zinc is prepared by a coprecipitation method or the like.
You. In particular, copper oxide-zinc oxide-aluminum oxide and
Ternary or quaternary catalyst made of chromium oxide and / or chromium oxide
It has high methanol synthesis activity and is widely used.
You. On the other hand, methanol is MTBE (methyl tertiary).
Butyl ether), gasoline, petrochemical intermediate products, and
To produce hydrogen, carbon monoxide, city gas, etc.
And the demand for fuel will increase in the future.
It is thought that a large methanol synthesis plant will be
It is expected to be built. Currently, methanol is naturally
Hydrogen and monoacid produced by gas steam reforming reaction
Using the gas containing carbonized carbon as a raw material,
It is manufactured by contact with a medium or the like. [0003] In addition to the above three- or four-component catalysts,
Catalyst consisting of copper oxide-zinc oxide-manganese oxide
6-9376), copper oxide-zinc oxide-silicon oxide
Catalyst (JP-B-63-29287), oxidation
Catalyst consisting of copper-zinc oxide-gallium oxide
Japanese Patent Application Publication No. 310138) has been proposed.
Low synthetic activity and long life
Development of a high-performance methanol synthesis catalyst is awaited
Have been. [0004] SUMMARY OF THE INVENTION Copper, zinc, aluminum
Catalysts composed of various oxides of methanol have high methanol synthesis activity
However, there is a problem that the activity decreases with time. The present invention
Is highly active and durable in view of the above technical standards
To provide a catalyst. [0005] Means for Solving the Problems The present inventors have developed an existing meta
Research and development of catalysts that exceed the performance of phenol synthesis catalysts
As a result, it plays the most important role in methanol synthesis activity.
Methanol with high dispersion of copper
The present inventors have found a synthesis catalyst and have completed the present invention. sand
That is, the present invention relates to hydrogen and carbon monoxide and / or carbon dioxide gas.
For synthesizing methanol from synthesis gas containing benzene
As at least copper, zinc, aluminum and gallium
Oxides, alkaline earth metal elements,
Contains one or more metal oxides of rare earth elements
What provides a methanol synthesis catalyst characterized by the following. [0006] BEST MODE FOR CARRYING OUT THE INVENTION
The preferred composition ratio (atomic ratio) is Cu: Zn: Al: Ga: α.
= 100: 10 to 200: 1 to 20: 1 to 20: 1 to 2
0. Where α is an alkaline earth metal element, a rare earth element
Indicates one or more metals of an element. Hereinafter, the production of the methanol synthesis catalyst of the present invention will be described.
An example of the method will be described in more detail. First, keep the precipitant aqueous solution warm
And stir the alkaline earth metal and rare earth elements while stirring.
Including one or more metals and each metal salt of Al, Ga and Zn
The aqueous solution is dropped to precipitate a precipitate, and after the drop, Cu
Is added dropwise to produce a precipitate. Dripping
When the pH at the end is 4 or more, most of the dropped metal ions
All precipitate as precipitates. The aqueous precipitant solution is an alkaline solution,
Usually, 0.1 to 10 M concentration of Na_TwoCO _ThreeAqueous solution, NaH
CO_ThreeAqueous solution, NaOH aqueous solution, K_TwoCO_ThreeAqueous solution, N
H_ThreeAn aqueous solution or the like is used._TwoCO_ThreeWater soluble
Liquids are preferred. Also, the temperature of the solution when forming the precipitate
It is preferable to keep the temperature in the range of 15 to 90 ° C. Furthermore, Cu, Zn, Al, Ga and Al
Potassium and rare earth metal salts are nitrates and salts.
At a concentration of 0.01-1.0M in the form of
Used as an aqueous solution, especially as a nitrate
Is preferred. In addition, the dropping time and the aging time are particularly
It has no effect on the activity of synthesis of tanol, but the metal ion
Any condition can be used as long as it disperses and precipitates, and usually drops
Duration: 1 minute to 3 hours, aging time: 1 minute to 3 hours
Will be applied. The resulting precipitate has various crystal seeds,
After thoroughly removing alkali metal ions and anions,
By baking in the range of 200 to 400 ° C., methanol
To obtain a synthesis catalyst. By using the catalyst of the present invention, methano
H as a synthesis gas as a raw material for_TwoAnd CO
Is H_TwoAnd CO and CO_TwoUse gas containing pressure:
200kg / cm^TwoG or less, temperature: 100-300 ° C
Long-term, stable performance
Can be achieved. [0011] The present invention will be more specifically described in the following examples.
Explain the effect of the catalyst of the present invention,
It is limited to the description of the embodiments unless the essence is impaired
is not. (Example 1) Sodium carbonate: 2.5mo
1 dissolved in 2 liters of water and kept at 60 ° C. This
The aqueous lukari solution is referred to as solution A. Zinc nitrate: 0.18mo
l and aluminum nitrate: 0.03 mol, gallium nitrate
System: 0.015 mol and magnesium nitrate: 0.01
5 mol dissolved in 600 cc of water, kept at 60 ° C,
This acidic solution is referred to as solution B. Further, copper nitrate: 0.3
mol was dissolved in 300 cc of water and kept at 60 ° C.
The acidic solution is referred to as solution C. First, 30 minutes of solution B is added to solution A while stirring.
Drops uniformly over minutes to obtain a suspension. Next, solution C
At a constant rate over 30 minutes,
Get the artifact. After lowering, aged for 2 hours, then sediment
Filtration and Na ion, NO _ThreeNo ions are detected
Wash. Furthermore, it was dried at 100 ° C. for 24 hours.
Methanol synthesis by baking at 300 ° C for 3 hours
Obtain a catalyst. This catalyst is referred to as catalyst 1. Magnesium nitrate
Use barium nitrate and stonium nitrate instead of
Except for the above, the same adjustments were made as for catalyst 1, and catalyst 2 and catalyst
3 was obtained. (Example 2) Zinc nitrate: 0.3 mol in solution B
1, aluminum nitrate: 0.05mol, gallium nitrate
System: 0.03 mol, calcium nitrate: 0.03 mol
Except that methanol was used.
A catalyst for the synthesis of the catalyst was prepared. This catalyst is referred to as catalyst 4. Sa
In addition, in solution B, zinc nitrate: 0.15 mol, aluminum nitrate
: 0.015mol, gallium nitrate: 0.015m
ol, cerium nitrate: 0.015 mol, and solution B
0.15 mol of zinc nitrate, 0.1 mol of aluminum nitrate.
006 mol, gallium nitrate: 0.006 mol, nitric acid
Lanthanum: Example except that 0.006 mol is used
Catalyst 5 and Catalyst 6 were obtained in the same manner as in Preparation Example 1. (Example 3) The same set as the catalyst 1 of Example 1
Using the solutions A, B, and C, the mixture of the solutions B and C is dissolved.
The contact was performed in the same manner as in Example 1 except that the solution was dropped into the liquid A.
Medium 7 was obtained. Example 4 Zinc nitrate in solution B: 0.15 m
ol, aluminum nitrate: 0.009 mol: gall nitrate
: 0.006 mol, magnesium nitrate: 0.00
6 mol, using lanthanum nitrate: 0.006 mol
Except for the above, a methanol synthesis catalyst was prepared in the same preparation method as in Example 1.
A medium was prepared. This catalyst is referred to as catalyst 8. Furthermore, liquid B
0.15 mol of zinc nitrate, 0.1 mol of aluminum nitrate.
009 mol, gallium nitrate: 0.006 mol, nitric acid
Lanthanum: 0.006 mol, neodymium nitrate: 0.0
Preparation method similar to that of Example 1 except that 06 mol was used
A methanol synthesis catalyst was prepared by the method. This catalyst was replaced with catalyst 9
And Comparative Example 1 In the preparation method of Example 1,
Gallium nitrate or
Similar except that no aluminum nitrate was added
The composition is CuO-ZnO-Al_TwoO_Three(Cu: Z
n: Al = 100: 60: 10) Catalyst 10 and CuO—
ZnO-Ga_TwoO_Three(Cu: Zn, Ga = 100: 6
0:10) of catalyst 11 was prepared. In addition, in the first embodiment,
In the manufacturing method, aluminum nitrate, gallium nitrate and
Instead of magnesium nitrate, use silica sol or
In the same manner except that a gun was used, the composition was CuO
-ZnO-SiO_Two(Cu: Zn: Si = 100: 6
0:10) catalyst 12 and CuO—ZnO—MnO_x(C
u: Zn: Mn = 100: 60: 10, x = 1.5-
Catalyst 13 of 2) was prepared. (Experimental Example 1) Obtained in Examples and Comparative Examples
Of the catalysts 1 to 13
The test was performed under the conditions shown in Table 1 below. [0019] [Table 1] The catalyst is sized to 16-28 mesh
Into a 2 cc microreactor,_Two3% / N_TwoBe
After reducing with source gas, supply the raw material gas
Activity evaluation was performed. Table 2 shows the initial activity evaluation results for each catalyst.
Show. [0021] [Table 2]The reaction products were all methanol and water. table
As shown in FIG. 2, the catalyst prepared according to the present invention is a conventional catalyst 1
Higher methanol synthesis activity than 0-13
Was. (Experimental example 2) Catalyst used for initial activity evaluation
1. Catalyst 9 was used as a catalyst for durability test. The reaction conditions are
Except for the reaction pressure, the procedure was the same as in Experimental Example 1. The activity results are shown in Table 3.
Show. [0023] [Table 3]The reaction products were all methanol and water. table
As shown in FIG. 3, the catalyst prepared in the present invention is different from the conventional catalyst.
Higher methanol synthesis activity and higher durability
Turned out to be. [0024] The methanol synthesis catalyst of the present invention is methanol
High synthetic activity and long-term activity
Therefore, methanol can be efficiently synthesized.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-8-1000 (JP, A) JP-A 64-27645 (JP, A) JP-A-58-104635 (JP, A) JP-A 8- 24648 (JP, A) Special table 58-501132 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C07B 61/00

Claims (1)

(57) [Claim 1] It contains at least each oxide of copper, zinc, aluminum and gallium, and further contains at least one metal oxide of an alkaline earth metal element and a rare earth element. A methanol synthesis catalyst, comprising: